JP2008056977A - Copper alloy and its production method - Google Patents

Copper alloy and its production method Download PDF

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JP2008056977A
JP2008056977A JP2006233962A JP2006233962A JP2008056977A JP 2008056977 A JP2008056977 A JP 2008056977A JP 2006233962 A JP2006233962 A JP 2006233962A JP 2006233962 A JP2006233962 A JP 2006233962A JP 2008056977 A JP2008056977 A JP 2008056977A
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copper alloy
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JP4943095B2 (en
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Takefumi Ito
武文 伊藤
Toshikazu Kawabata
俊和 川畑
Yuujitsushi Iwashita
由実子 岩下
Toshihiro Kurita
敏広 栗田
Takayuki Nagai
貴之 永井
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Melco Metecs Corp
Mitsubishi Electric Corp
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Mitsubishi Electric Corp
Mitsubishi Electric Metex Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/026—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent

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Abstract

<P>PROBLEM TO BE SOLVED: To provide a copper alloy having tensile strength of ≥700 N/mm<SP>2</SP>and electrical conductivity of ≥60%IACS. <P>SOLUTION: Regarding the copper alloy having a composition comprising, by mass, 0.8 to 1.8% Co, 0.16 to 0.6% Si, and the balance Cu with inevitable impurities, the mass ratio (Co/Si) between the Co and Si is 3.0 to 5.0, further, the size of inclusions precipitated into the copper alloy is ≤2 μm, and also, the volume of the inclusions with a size of 0.05 to 2 μm in the copper alloy is ≤0.5%. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、銅合金及びその製造方法に関し、特に電子部品用の銅合金及びその製造方法に関する。   The present invention relates to a copper alloy and a manufacturing method thereof, and more particularly to a copper alloy for electronic components and a manufacturing method thereof.

ＩＣ（集積回路）を搭載するリードフレームや電子機器に使用されるコネクタ端子等では、適用機器の小型化や多機能化、実装面密度の高密度化に伴い、リードフレームの薄板化、端子の多ピン化及び狭ピッチ化が進んでいる。このため、かかる電子部品の実装時における接続の信頼性が強く求められようになってきている。
すなわち、このような電子部品用の金属材料においては、電子部品の小型化が進むにつれて薄板化されるために強度をより一層向上させる必要があると共に、多ピン化及び狭ピッチ化が進むにつれて断面積が小さくなるために導電性をより一層向上させる必要がある。 With lead frames mounted on ICs (integrated circuits) and connector terminals used in electronic equipment, as the size of applied equipment becomes smaller and multifunctional, and the mounting surface density increases, the lead frame becomes thinner, The number of pins and the pitch are being reduced. For this reason, there is a strong demand for connection reliability when mounting such electronic components.
That is, in such a metal material for electronic parts, it is necessary to further improve the strength because it is made thinner as electronic parts become smaller, and as the number of pins and the pitch become narrower, the metal materials for electronic parts are cut off. In order to reduce the area, it is necessary to further improve the conductivity.

高強度と高導電性とを兼ね備えた電子部品用金属材料としては、従来、銅（Ｃｕ）にベリリウム（Ｂｅ）を添加した合金材料が知られている。かかる合金材料の中には、８００Ｎ／ｍｍ２以上の高い引張強度、及び５０％ＩＡＣＳ（International Annealed Copper Standard）以上の高い導電率の両方を有するものもある。
しかしながら、最近の環境問題への配慮から、Ｂｅを含有する合金材料の使用が避けられるようになってきた。そこで、これらの合金材料に代わる銅合金が注目されている。 As a metal material for electronic parts having both high strength and high conductivity, an alloy material in which beryllium (Be) is added to copper (Cu) is conventionally known. Some such alloy materials have both a high tensile strength of 800 N / mm 2 or higher and a high conductivity of 50% IACS (International Annealed Copper Standard) or higher.
However, due to recent considerations for environmental problems, the use of alloy materials containing Be has been avoided. Therefore, copper alloys that replace these alloy materials have attracted attention.

銅合金の中でもＣｕ−Ｃｏ−Ｓｉ系合金は、微細なＣｏ２Ｓｉ金属間化合物がＣｕ内に分散析出し、転移の障壁となることによって、強度及び導電性を向上させる析出硬化型の合金であることが判っている。これまでに、Ｃｏ及びＳｉの添加量を調節したり、微量の添加材をさらに添加することによって、強度及び導電性をより一層向上させ得ることが報告されている。 Among the copper alloys, Cu—Co—Si based alloys are precipitation hardening type alloys that improve strength and conductivity by dispersing and precipitating fine Co 2 Si intermetallic compounds in Cu and becoming barriers to transition. I know that there is. So far, it has been reported that the strength and conductivity can be further improved by adjusting the addition amount of Co and Si or further adding a small amount of additive.

かかる従来のＣｕ−Ｃｏ−Ｓｉ系合金としては、０．４重量％以上１．６重量％以下のＣｏ及び０．１重量％以上０．５重量％以下のＳｉを含有し、残部がＣｕ及び不可避的不純物で構成される銅合金に、０．０５重量％以上１．０重量％以下のＺｎや、Ｃａ、Ｙ、希土類元素、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ及びＮｂのうち少なくとも１種を内割りで０．０００５重量％以上０．１重量％以下さらに含有させたリードフレーム用銅合金がある（例えば、特許文献１参照）。
また、０．１重量％以上３．０重量％以下のＣｏ、０．３重量％以上１．０重量％以下のＳｉ、０．３重量％以上１．０重量％以下のＺｎ、０．００５重量％以上０．１重量％以下のＭｎ及び０．００５重量％以上０．１重量％以下のＰを含有し、残部がＣｕ及び不可避的不純物で構成される銅合金において、母相中にＣｏとＳｉとの化合物及びＣｏとＰとの化合物が存在し、且つ母相の平均結晶粒度が２０μｍ以下で、圧延方向に対する板厚方向のアスペクト比が１以上３以下である電子電気部品用銅合金がある（例えば、特許文献２参照）。 Such a conventional Cu—Co—Si based alloy contains 0.4 wt% or more and 1.6 wt% or less of Co and 0.1 wt% or more and 0.5 wt% or less of Si, with the balance being Cu and The copper alloy composed of inevitable impurities contains at least one of Zn, Ca, Y, rare earth elements, Ti, Zr, Hf, V, and Nb in an amount of 0.05 wt% to 1.0 wt%. There is a copper alloy for lead frames that further contains 0.0005% by weight or more and 0.1% by weight or less by splitting (see, for example, Patent Document 1).
Further, 0.1 wt% or more and 3.0 wt% or less of Co, 0.3 wt% or more and 1.0 wt% or less of Si, 0.3 wt% or more and 1.0 wt% or less of Zn, 0.005 In a copper alloy containing not less than 0.1% by weight and not more than 0.1% by weight of Mn and not less than 0.005% by weight and not more than 0.1% by weight of P, with the balance being Cu and inevitable impurities, And Si and a compound of Co and P, the average crystal grain size of the parent phase is 20 μm or less, and the aspect ratio in the plate thickness direction with respect to the rolling direction is 1 or more and 3 or less. (See, for example, Patent Document 2).

特開平２−２７７７３５号公報JP-A-2-277735 特開平９−２０９４３号公報JP-A-9-20943

しかしながら、従来の銅合金では、Ｃｏ、Ｓｉ及びその他の元素の添加量、並びにＣｏ／Ｓｉ比が最適化されていなかったり、銅合金が適切な組織構造を有していないために、強度及び導電性の両方に優れるものは得られなかった。例えば、特許文献１及び２では、銅合金の組成については検討がなされているものの、銅合金中に析出する介在物については検討がなされていないため、銅合金が適切な組織構造を有しておらず、強度及び導電性のいずれかの特性が十分でないという問題があった。そのため、従来の銅合金では、７００Ｎ／ｍｍ２以上の引張強度と同時に６０％ＩＡＣＳ以上の導電率を得ることはできなかった。
本発明は、上記のような問題を解決するためになされたものであり、強度及び導電性の両方に優れる、具体的には、７００Ｎ／ｍｍ２以上の引張強度及び６０％ＩＡＣＳ以上の導電率を有する銅合金を提供することを目的とする。
また、本発明は、上記特性を有する銅合金の製造方法を提供することを目的とする。 However, in conventional copper alloys, the addition amount of Co, Si and other elements, and the Co / Si ratio are not optimized, and the copper alloy does not have an appropriate structure, so that strength and conductivity Nothing superior in both properties was obtained. For example, in Patent Documents 1 and 2, although the copper alloy composition has been studied, the inclusions that precipitate in the copper alloy have not been studied, so the copper alloy has an appropriate structure. In addition, there is a problem that either the strength or the conductivity is not sufficient. Therefore, with a conventional copper alloy, it was not possible to obtain a conductivity of 60% IACS or more simultaneously with a tensile strength of 700 N / mm 2 or more.
The present invention has been made to solve the above problems, and is excellent in both strength and conductivity. Specifically, it has a tensile strength of 700 N / mm 2 or more and a conductivity of 60% IACS or more. It aims at providing the copper alloy which has this.
Moreover, this invention aims at providing the manufacturing method of the copper alloy which has the said characteristic.

そこで、本発明者らは上記のような問題を解決すべく鋭意研究した結果、銅合金の組成と共に、銅合金中に析出する介在物の大きさ及び総量を最適化することで、銅合金の組織構造を最適化し得ることに想到し、本発明を完成するに至った。
すなわち、本発明は、０．８質量％以上１．８質量％以下のＣｏ及び０．１６質量％以上０．６質量％以下のＳｉを含有し、残部がＣｕ及び不可避的不純物で構成される銅合金であって、前記Ｃｏと前記Ｓｉとの質量比（Ｃｏ／Ｓｉ）が３．０以上５．０以下であると共に、前記銅合金中に析出する介在物の大きさが２μｍ以下であり、且つ前記銅合金における０．０５μｍ以上２μｍ以下の大きさの介在物が０．５容積％以下であることを特徴とする銅合金である。
また、本発明は、（ａ）０．８質量％以上１．８質量％以下のＣｏ及び０．１６質量％以上０．６質量％以下のＳｉを含有し、残部がＣｕ及び不可避的不純物で構成され、且つ前記Ｃｏと前記Ｓｉとの質量比（Ｃｏ／Ｓｉ）が３．０以上５．０以下である銅合金原料を溶解して鋳塊を形成した後、前記鋳塊を圧延する工程と、（ｂ）前記圧延材を７００℃以上１０００℃以下に加熱した後に急冷する溶体化処理を施す工程と、（ｃ）前記溶体化処理後の合金素材を４００℃以上６００℃以下で２時間以上８時間以下加熱する時効処理を施す工程と、（ｄ）前記時効処理後の合金素材を、少なくとも３８０℃までは１０℃／ｈ以上５０℃／ｈ以下の冷却速度で冷却する工程と、（ｅ）前記冷却後の合金素材を冷間圧延して仕上げる工程とを含むことを特徴とする銅合金の製造方法である。 Therefore, as a result of intensive studies to solve the above-mentioned problems, the present inventors have optimized the size and total amount of inclusions precipitated in the copper alloy together with the composition of the copper alloy. The inventors have conceived that the organizational structure can be optimized, and have completed the present invention.
That is, the present invention contains 0.8% by mass or more and 1.8% by mass or less Co and 0.16% by mass or more and 0.6% by mass or less Si, with the balance being Cu and inevitable impurities. It is a copper alloy, and the mass ratio (Co / Si) between Co and Si is 3.0 or more and 5.0 or less, and the size of inclusions precipitated in the copper alloy is 2 μm or less. The inclusions having a size of 0.05 μm or more and 2 μm or less in the copper alloy are 0.5% by volume or less.
Moreover, this invention contains (a) 0.8 mass% or more and 1.8 mass% or less of Co and 0.16 mass% or more and 0.6 mass% or less of Si, with the remainder being Cu and inevitable impurities. A step of forming the ingot by melting a copper alloy raw material that is configured and has a mass ratio (Co / Si) of Co to Si of 3.0 to 5.0 and then rolling the ingot And (b) a step of performing a solution treatment in which the rolled material is heated to 700 ° C. or more and 1000 ° C. or less and then rapidly cooled, and (c) the alloy material after the solution treatment is treated at 400 ° C. or more and 600 ° C. or less for 2 hours. (D) a step of cooling the alloy material after the aging treatment at a cooling rate of 10 ° C./h or more and 50 ° C./h or less to at least 380 ° C .; e) a step of cold rolling and finishing the cooled alloy material A method for producing a copper alloy characterized by and.

本発明によれば、銅合金中において、最適な析出量のＣｏ２Ｓｉ化合物を含有させ得ると共に、固溶状態で残るＣｏ及びＳｉ元素の含有量を低減させ得るので、強度及び導電性の両方に優れた、すなわち、７００Ｎ／ｍｍ２以上の引張強度及び６０％ＩＡＣＳ以上の導電率を有する銅合金を提供することができる。 According to the present invention, in the copper alloy, an optimal precipitation amount of the Co 2 Si compound can be contained, and the content of Co and Si elements remaining in a solid solution state can be reduced. In other words, a copper alloy having excellent tensile strength of 700 N / mm 2 or more and conductivity of 60% IACS or more can be provided.

実施の形態１．
（銅合金）
本発明の銅合金は、０．８質量％以上１．８質量％以下のＣｏ及び０．１６質量％以上０．６質量％以下のＳｉを含有し、残部がＣｕ及び不可避的不純物で構成される。Ｃｏの含有量が０．８質量％未満であるか、又はＳｉの含有量が０．１６質量％未満であると、十分な量のＣｏ２Ｓｉ化合物が生じず、所望の強度及び導電性が得られない。一方、Ｃｏの含有量が１．８質量％を超えるか、又はＳｉの含有量が０．６質量％を超えると、Ｃｏ−Ｓｉ化合物相やＣｕ−Ｃｏ−Ｓｉ合金相が多く析出してしまい、所望の強度及び導電性が得られない。
また、ＣｏとＳｉとの質量比（Ｃｏ／Ｓｉ）は、３．０以上５．０以下の範囲である。かかる質量比が３．０未満であるか、又は５．０を超えると、Ｃｏ２Ｓｉ化合物以外のＣｏ−Ｓｉ化合物相やＣｕ−Ｃｏ−Ｓｉ合金相が多く析出してしまい、所望の強度及び導電性が得られない。
ここで、本発明における不可避的不純物とは、通常の地金中に含まれるもの、又は銅合金の製造中に混入する不純物を意味し、例えば、Ａｓ，Ｓｂ、Ｂｉ、Ｐｂ、Ｓ、Ｆｅ、Ｏ２及びＨ２等が挙げられる。これらの中でも、本発明の銅合金では、メッキ密着性及び半田付け性を向上させる観点から、Ｏ２含有量が１０ｐｐｍ以下、及びＨ２含有量が１ｐｐｍ以下であることが好ましい。Ｏ２含有量が１０ｐｐｍを超えると、メッキ密着性及び半田付け性が低下することがある。また、Ｈ２含有量が１ｐｐｍを超えると、メッキ密着性及び半田付け性が低下することがある。 Embodiment 1 FIG.
(Copper alloy)
The copper alloy of the present invention contains 0.8 mass% or more and 1.8 mass% or less of Co and 0.16 mass% or more and 0.6 mass% or less of Si, with the balance being composed of Cu and inevitable impurities. The When the Co content is less than 0.8% by mass or the Si content is less than 0.16% by mass, a sufficient amount of the Co 2 Si compound is not generated, and the desired strength and conductivity are obtained. I can't get it. On the other hand, when the Co content exceeds 1.8% by mass or the Si content exceeds 0.6% by mass, many Co—Si compound phases and Cu—Co—Si alloy phases are precipitated. The desired strength and conductivity cannot be obtained.
The mass ratio (Co / Si) between Co and Si is in the range of 3.0 to 5.0. When the mass ratio is less than 3.0 or exceeds 5.0, a large amount of Co—Si compound phase or Cu—Co—Si alloy phase other than the Co 2 Si compound is precipitated, and the desired strength and Conductivity cannot be obtained.
Here, the inevitable impurities in the present invention mean impurities contained in normal metal or impurities mixed during the production of a copper alloy. For example, As, Sb, Bi, Pb, S, Fe, Examples include O 2 and H 2 . Among these, in the copper alloy of the present invention, it is preferable that the O 2 content is 10 ppm or less and the H 2 content is 1 ppm or less from the viewpoint of improving plating adhesion and solderability. When the O 2 content exceeds 10 ppm, plating adhesion and solderability may be deteriorated. Further, when containing H 2 content exceeds 1 ppm, the plating adhesion and solderability may be deteriorated.

また、本発明の銅合金中には介在物が析出しており、その介在物の大きさは２μｍ以下である。かかる介在物の大きさが２μｍを超えると、所望の強度が得られないと共に、メッキ密着性が低下してしまう。
ここで、本発明における介在物とは、銅合金の製造中に生じる粗大な析出粒子を意味し、具体的には、大気との反応による酸化物や、微細なＣｏ２Ｓｉ化合物以外の好ましくないＣｏ−Ｓｉ化合物相又はＣｕ−Ｃｏ−Ｓｉ合金相による粒子を意味する。
また、介在物の大きさとは、球形であればその直径の寸法を意味し、楕円形又は矩形であれば短直径又は短辺の寸法を意味する。 In addition, inclusions are precipitated in the copper alloy of the present invention, and the size of the inclusions is 2 μm or less. When the size of the inclusions exceeds 2 μm, desired strength cannot be obtained and plating adhesion is deteriorated.
Here, the inclusions in the present invention mean coarse precipitate particles generated during the production of a copper alloy. Specifically, the inclusions are not preferable except for oxides by reaction with the atmosphere and fine Co 2 Si compounds. The particle | grains by a Co-Si compound phase or a Cu-Co-Si alloy phase are meant.
The size of the inclusion means a dimension of the diameter if it is a sphere, and a dimension of a short diameter or a short side if it is an ellipse or a rectangle.

さらに、本発明の銅合金において、０．０５μｍ以上２μｍ以下の大きさの介在物は０．５容積％以下である。かかる介在物が０．５容積％を超えると、所望の強度が得られないと共に、メッキ密着性が低下してしまう。
ここで、本発明の銅合金における介在物の容積比は、本発明の銅合金の断面を研磨し、当該研磨面を走査電子顕微鏡により観察して求めることができるが、この場合の観察領域は、試料最表面から所定の深さ（例えば、約１μｍ）以上の領域とし、当該観察領域内の介在物の全面積を画像処理により積算し、観察領域内で割り出して求めることができる。具体的には、１００μｍ角程度の観察領域を任意に５箇所観察し、各観察領域の介在物の面積比を平均した値を介在物の容積比とした。 Furthermore, in the copper alloy of the present invention, inclusions having a size of 0.05 μm or more and 2 μm or less are 0.5% by volume or less. When such inclusions exceed 0.5% by volume, the desired strength cannot be obtained and the plating adhesion is deteriorated.
Here, the volume ratio of inclusions in the copper alloy of the present invention can be determined by polishing the cross section of the copper alloy of the present invention and observing the polished surface with a scanning electron microscope. A region having a predetermined depth (for example, about 1 μm) or more from the outermost surface of the sample can be obtained by integrating the total area of inclusions in the observation region by image processing and calculating the total in the observation region. Specifically, the observation area of about 100 μm square was arbitrarily observed at five locations, and the value obtained by averaging the area ratio of inclusions in each observation area was defined as the volume ratio of inclusions.

本発明の銅合金は、メッキ密着性を向上させる観点からＺｎを含有することができる。かかるＺｎは、Ｓｎ（スズ）メッキ及びＳｎ合金メッキ後の経時変化による界面剥離を抑制する効果を有している。Ｚｎの含有量は、０．１質量％以上１．０質量％以下であることが好ましい。このような範囲であれば、銅合金の強度及び導電性を損なうことなく、メッキ密着性を向上させることができる。Ｚｎの含有量が０．１質量％未満であると、Ｚｎの添加によるメッキ密着性の向上効果が得られないことがある。一方、Ｚｎの含有量が１．０質量％を超えると、導電性が低下してしまうことがある。   The copper alloy of the present invention can contain Zn from the viewpoint of improving plating adhesion. Such Zn has an effect of suppressing interfacial peeling due to a change with time after Sn (tin) plating and Sn alloy plating. The Zn content is preferably 0.1% by mass or more and 1.0% by mass or less. If it is such a range, plating adhesiveness can be improved, without impairing the intensity | strength and electroconductivity of a copper alloy. If the Zn content is less than 0.1% by mass, the effect of improving the plating adhesion due to the addition of Zn may not be obtained. On the other hand, if the Zn content exceeds 1.0% by mass, the conductivity may decrease.

本発明の銅合金は、強度をより一層向上させる観点から、Ｆｅ、Ｎｉ、Ｐ、Ｓｎ、Ｍｇ、Ｚｒ、Ｃｒ又はＭｎの１種以上を含有することができる。この中でも、Ｆｅ及びＮｉは、結晶粒の微細化によって曲げ加工性を向上させる効果もあるのでより好ましい。かかる元素の含有量は、総量で０．０１質量％以上０．２質量％以下であることが好ましい。かかる元素の配合量が０．０１質量％未満であると、かかる元素の添加による強度の向上効果が得られないことがある。一方、かかる元素の配合量が０．２質量％を超えると、導電性が低下してしまうことがある。   The copper alloy of the present invention can contain one or more of Fe, Ni, P, Sn, Mg, Zr, Cr, or Mn from the viewpoint of further improving the strength. Among these, Fe and Ni are more preferable because they have an effect of improving bending workability by refining crystal grains. The total content of such elements is preferably 0.01% by mass or more and 0.2% by mass or less. If the blending amount of such an element is less than 0.01% by mass, the effect of improving the strength due to the addition of such an element may not be obtained. On the other hand, if the amount of such elements exceeds 0.2% by mass, the conductivity may be lowered.

（銅合金の製造方法）
従来の銅合金の製造方法では、銅合金原料を溶解して鋳造することによって得られた鋳塊を熱間圧延した後、冷間圧延等を行うことで、銅合金中に格子欠陥を生じさせている。
例えば、特許文献１の銅合金の製造方法では、銅合金原料を溶解して金型に鋳造することによって所望寸法の鋳塊を得た後、その鋳塊を９５０℃で熱間圧延し、直ちに水冷する。続いて、熱間圧延板の表面を面削し、所望板厚まで冷間圧延し、５００℃で１時間の熱処理後に再度所望厚さに圧延して３００℃で１時間のひずみ取り焼鈍を行っている。
また、特許文献２の銅合金の製造方法では、銅合金原料を溶解して鋳造することによって所望寸法の鋳塊を得た後、その鋳塊を９８０℃で３時間保持し、次いで熱間圧延を行い、熱間圧延後に面削又は酸洗バフ研磨を行い所望寸法とする。続いて、８５％以上の冷間圧延を施し、４５０℃以上４８０℃以下の温度で５分以上３０分以下の間焼鈍させた後、３０％以下の冷間圧延を施し、更に４５０℃以上５００℃以下の温度で３０分以上１２０分以下の間、時効処理を行っている。 (Copper alloy manufacturing method)
In the conventional method for producing a copper alloy, after hot rolling an ingot obtained by melting and casting a copper alloy raw material, cold rolling or the like is performed to cause lattice defects in the copper alloy. ing.
For example, in the method for producing a copper alloy disclosed in Patent Document 1, an ingot having a desired size is obtained by melting a copper alloy raw material and casting it into a mold, and then hot-rolling the ingot at 950 ° C. immediately. Cool with water. Subsequently, the surface of the hot-rolled plate is chamfered, cold-rolled to a desired plate thickness, heat-treated at 500 ° C. for 1 hour, rolled again to the desired thickness, and subjected to strain relief annealing at 300 ° C. for 1 hour. ing.
Moreover, in the manufacturing method of the copper alloy of patent document 2, after obtaining the ingot of a desired dimension by melt | dissolving and casting a copper alloy raw material, the ingot is hold | maintained at 980 degreeC for 3 hours, Then, it hot-rolls. After hot rolling, chamfering or pickling buffing is performed to obtain a desired dimension. Subsequently, the steel sheet is subjected to cold rolling of 85% or more, annealed at a temperature of 450 ° C. or higher and 480 ° C. or lower for 5 minutes or longer and 30 minutes or shorter, and then subjected to cold rolling of 30% or lower, and further 450 ° C. or higher and 500 ° C. or higher. An aging treatment is performed at a temperature of 30 ° C. or lower for 30 minutes to 120 minutes.

一方、本発明者らは、上記特性を有する銅合金の製造方法について鋭意研究した結果、熱間圧延後の冷間圧延等による格子欠陥の導入が重要ではなく、時効処理後の冷却を１０℃／ｈ以上５０℃／ｈ以下の冷却速度で、少なくとも３８０℃まで冷却することが銅合金の強度及び導電性を向上させる上で重要であることを見出した。
さらに詳細に説明すると、本発明者らは、溶体化処理後の急冷により銅合金には十分な格子欠陥が導入されており、新たに冷間圧延等による歪を与えることは不要であることを見出した。その一方で、発明者らの試行により、冷間圧延等を行わず、時効処理後の冷却速度を１０℃／ｈ以上５０℃／ｈ以下とすることにより、Ｃｏ２Ｓｉ化合物の十分な量の析出がなされると共に、銅合金に残余歪を残さないという効果があることを見出した。 On the other hand, as a result of earnest research on the manufacturing method of the copper alloy having the above characteristics, the present inventors have found that introduction of lattice defects by cold rolling after hot rolling is not important, and cooling after aging treatment is performed at 10 ° C. It was found that cooling to at least 380 ° C. at a cooling rate of 50 ° C./h to 50 ° C./h is important for improving the strength and conductivity of the copper alloy.
More specifically, the present inventors have found that sufficient lattice defects have been introduced into the copper alloy by rapid cooling after the solution treatment, and it is not necessary to newly give a strain due to cold rolling or the like. I found it. On the other hand, by the inventors' trial, a sufficient amount of the Co 2 Si compound can be obtained by not performing cold rolling or the like and setting the cooling rate after the aging treatment to 10 ° C./h or more and 50 ° C./h or less. It has been found that there is an effect that precipitation is made and no residual strain is left in the copper alloy.

すなわち、本発明の銅合金の製造方法は、（ａ）０．８質量％以上１．８質量％以下のＣｏ及び０．１６質量％以上０．６質量％以下のＳｉを含有し、残部がＣｕ及び不可避的不純物で構成され、且つ前記Ｃｏと前記Ｓｉとの質量比（Ｃｏ／Ｓｉ）が３．０以上５．０以下である銅合金原料を溶解して鋳塊を形成した後、前記鋳塊を圧延する工程と、（ｂ）前記圧延材を７００℃以上１０００℃以下に加熱した後に急冷する溶体化処理を施す工程と、（ｃ）前記溶体化処理後の合金素材を４００℃以上６００℃以下で２時間以上８時間以下加熱する時効処理を施す工程と、（ｄ）前記時効処理後の合金素材を、少なくとも３８０℃までは１０℃／ｈ以上５０℃／ｈ以下の冷却速度で冷却する工程と、（ｅ）前記冷却後の合金素材を冷間圧延して仕上げる工程とを含む。   That is, the method for producing a copper alloy of the present invention comprises (a) 0.8 mass% to 1.8 mass% Co and 0.16 mass% to 0.6 mass% Si, with the balance being After the copper alloy raw material composed of Cu and inevitable impurities and having a mass ratio of Co to Si (Co / Si) of 3.0 or more and 5.0 or less to form an ingot, A step of rolling the ingot, a step of (b) performing a solution treatment for rapidly cooling the rolled material after heating to 700 ° C. or more and 1000 ° C. or less, and (c) a temperature of 400 ° C. or more for the alloy material after the solution treatment. A step of performing an aging treatment of heating at 600 ° C. or less for 2 hours or more and 8 hours or less, and (d) the alloy material after the aging treatment at a cooling rate of 10 ° C./h or more and 50 ° C./h or less to at least 380 ° C. And (e) cold rolling the cooled alloy material. And a step to finish.

（ａ）工程において、銅合金原料としては、メッキ密着性を向上させる観点から、０．１質量％以上１．０質量％以下のＺｎをさらに配合することもできる。かかる配合量とする理由は、上述の通りである。
さらに、銅合金原料として、強度をより一層向上させる観点から、Ｆｅ、Ｎｉ、Ｐ、Ｓｎ、Ｍｇ、Ｚｒ、Ｃｒ又はＭｎのうちの１種以上を総量で０．０１質量％以上０．２質量％以下配合することもできる。かかる配合量とする理由は、上述の通りである。
また、上記銅合金原料は、メッキ密着性及び半田付け性を向上させる観点から、Ｏ２含有量を１０ｐｐｍ以下、及びＨ２含有量を１ｐｐｍ以下とすることが好ましい。かかる含有量とする理由は、上述の通りである。かかる銅合金原料においてＯ２及びＨ２含有量を低減させる方法としては、特に限定されることはなく、公知の方法を用いることができる。かかる方法としては、例えば、ホウ化カルシウム等の脱酸剤を使用するか、又はアルゴンガスや窒素ガス等を用いてバブリング処理を行えばよい。 In the step (a), as a copper alloy raw material, 0.1% by mass or more and 1.0% by mass or less of Zn can be further blended from the viewpoint of improving plating adhesion. The reason for the blending amount is as described above.
Furthermore, as a copper alloy raw material, from the viewpoint of further improving the strength, one or more of Fe, Ni, P, Sn, Mg, Zr, Cr, or Mn is 0.01% by mass or more and 0.2% by mass in total. % Or less can also be blended. The reason for the blending amount is as described above.
The copper alloy raw material preferably has an O 2 content of 10 ppm or less and an H 2 content of 1 ppm or less from the viewpoint of improving plating adhesion and solderability. The reason for the content is as described above. The method for reducing the O 2 and H 2 contents in such a copper alloy raw material is not particularly limited, and a known method can be used. As such a method, for example, a deoxidizer such as calcium boride may be used, or bubbling may be performed using argon gas, nitrogen gas, or the like.

また、上記銅合金原料を溶解する方法としては、特に制限されることはなく、高周波溶解炉等の公知の装置を用いて、銅合金原料の融点以上の温度に加熱すればよい。さらに、鋳造及び圧延の方法としては、特に制限されることはなく、公知の方法に従って行うことができる。
なお、（ａ）工程中、鋳塊のスケールを除去する観点から、鋳塊を形成した後に面削を行ってもよい。また、（ａ）工程後に、合金を軟化させて加工性を向上させる等の観点から焼鈍を行ってもよい。かかる面削及び焼鈍の方法は、特に制限されることはなく、公知の方法に従って行うことができる。 The method for melting the copper alloy raw material is not particularly limited, and may be heated to a temperature equal to or higher than the melting point of the copper alloy raw material using a known apparatus such as a high-frequency melting furnace. Further, the casting and rolling methods are not particularly limited, and can be performed according to known methods.
In addition, during the step (a), from the viewpoint of removing the scale of the ingot, chamfering may be performed after the ingot is formed. Moreover, you may anneal from a viewpoint of softening an alloy and improving workability after the (a) process. Such chamfering and annealing methods are not particularly limited, and can be performed according to known methods.

（ｂ）工程における溶体化処理では、圧延材を７００℃以上１０００℃以下に加熱した後に急冷する。ここで、加熱時間は、１分以上６０分以下であることが好ましい。かかる加熱温度及び時間であれば、合金元素の良好な固溶化が達成される。また、加熱及び急冷の方法は、特に制限されることはなく、公知の方法に従って行えばよい。
（ｃ）工程における時効処理では、液体化処理後の合金素材を４００℃以上６００℃以下で２時間以上８時間以下加熱する。かかる加熱温度及び時間であれば、微細なＣｏ２Ｓｉ化合物が析出した状態を得ることができる。また、加熱の方法は、特に制限されることはなく、公知の方法に従って行えばよい。 In the solution treatment in the step (b), the rolled material is rapidly cooled after being heated to 700 ° C. or higher and 1000 ° C. or lower. Here, the heating time is preferably from 1 minute to 60 minutes. With such heating temperature and time, satisfactory solid solution of the alloy element is achieved. Moreover, the method of heating and quenching is not particularly limited, and may be performed according to a known method.
In the aging treatment in the step (c), the alloy material after the liquefaction treatment is heated at 400 ° C. or more and 600 ° C. or less for 2 hours or more and 8 hours or less. With such heating temperature and time, it is possible to obtain a state in which a fine Co 2 Si compound is precipitated. Further, the heating method is not particularly limited, and may be performed according to a known method.

（ｄ）工程では、時効処理後の合金素材を、少なくとも３８０℃まで１０℃／ｈ以上５０℃／ｈ以下の冷却速度で冷却する。
かかる範囲の冷却速度であれば、十分な量のＣｏ２Ｓｉ化合物が析出し、銅合金に残余歪を残さなくすることができる。かかる冷却速度が１０℃／ｈ未満であると、Ｃｏ２Ｓｉ化合物が粗大化するため、所望の強度が得られない。一方、かかる冷却速度が５０℃／ｈを超えると、銅合金に残余歪が残り、この歪によってＣｏ２Ｓｉ化合物の析出量が少なくなってＣｏ及びＳｉがそのまま固溶状態として残存するため、所望の強度及び導電性が得られない。
また、かかる冷却温度が３８０℃超過までであると、適切な銅合金の組織構造が得られず、所望の強度及び導電性が得られない。なお、かかる冷却温度が３８０℃に達した後は、その後の冷却過程によって銅合金の組織構造が大きく変化することはないため、かかる冷却温度の下限は特に制限されないが、適切な組織構造の銅合金を安定して得る観点から、３５０℃までは１０℃／ｈ以上５０℃／ｈ以下の冷却速度で冷却することがより好ましい。 In the step (d), the alloy material after the aging treatment is cooled to at least 380 ° C. at a cooling rate of 10 ° C./h or more and 50 ° C./h or less.
When the cooling rate is within such a range, a sufficient amount of the Co 2 Si compound is precipitated, and no residual strain can be left in the copper alloy. When the cooling rate is less than 10 ° C./h, the Co 2 Si compound is coarsened, so that a desired strength cannot be obtained. On the other hand, if the cooling rate exceeds 50 ° C./h, residual strain remains in the copper alloy, and the amount of precipitation of the Co 2 Si compound decreases due to this strain, and Co and Si remain in a solid solution state. Strength and conductivity cannot be obtained.
Further, if the cooling temperature is higher than 380 ° C., an appropriate structure of the copper alloy cannot be obtained, and desired strength and conductivity cannot be obtained. After the cooling temperature reaches 380 ° C., the structure of the copper alloy is not greatly changed by the subsequent cooling process. Therefore, the lower limit of the cooling temperature is not particularly limited, but the copper having an appropriate structure is used. From the viewpoint of obtaining an alloy stably, it is more preferable to cool to 350 ° C. at a cooling rate of 10 ° C./h or more and 50 ° C./h or less.

（ｅ）工程では、合金素材を冷間圧延することによって所望の大きさの銅合金に仕上げる。かかる冷間圧延の方法は、特に制限されることはなく、公知の方法に従って行えばよい。また、（ｅ）工程後には、銅合金の歪取りを行う観点から低温焼鈍を行ってもよい。かかる低温焼鈍の方法は、特に制限されることはなく、公知の方法に従って行うことができる。   In the step (e), a copper alloy having a desired size is finished by cold rolling the alloy material. The cold rolling method is not particularly limited, and may be performed according to a known method. In addition, after step (e), low-temperature annealing may be performed from the viewpoint of removing strain from the copper alloy. Such a low-temperature annealing method is not particularly limited and can be performed according to a known method.

このような製造方法によって得られる銅合金は、銅合金中に析出するＣｏ２Ｓｉ化合物の粗大化を抑制しつつ、十分な量の微細なＣｏ２Ｓｉ化合物を析出させることができるため、強度及び導電性に優れたものとなる。 The copper alloy obtained by such a manufacturing method can precipitate a sufficient amount of fine Co 2 Si compound while suppressing the coarsening of the Co 2 Si compound precipitated in the copper alloy. Excellent conductivity.

以下、実施例を示して本発明を具体的に説明するが、本発明は下記の実施例に限定されるものではない。
実施例及び比較例で得られた銅合金の下記の特性評価は、次の手順に従った。
（１）引張強度
引張強度の評価は、ＪＩＳ Ｚ２２４１に準拠して室温にて行った。
（２）導電率
導電率の評価は、ＪＩＳ Ｈ０５０５に準拠して室温にて行った。
（３）メッキ密着性
メッキ密着性の評価は、銅合金に厚さ３μｍの電気Ｓｎメッキを施し、１０５℃で５００時間（実施例４のみ５００時間及び１０００時間）の加熱を行った後、１８０度の折り曲げ、曲げ戻し試験を行い、試料表面を目視で観察することによって行った。かかる評価においては、メッキ膜が全く損傷していないものを○、メッキ膜は剥離していないが、損傷が認められるものを△、メッキ膜が剥離したものを×として表した。 EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated concretely, this invention is not limited to the following Example.
The following characteristics evaluation of the copper alloy obtained by the Example and the comparative example followed the following procedure.
(1) Tensile strength The tensile strength was evaluated at room temperature in accordance with JIS Z2241.
(2) Conductivity Conductivity was evaluated at room temperature in accordance with JIS H0505.
(3) Plating adhesion The plating adhesion was evaluated by applying electrical Sn plating with a thickness of 3 μm to a copper alloy and heating it at 105 ° C. for 500 hours (500 hours and 1000 hours only in Example 4). The bending and unbending tests were performed, and the sample surface was visually observed. In this evaluation, the case where the plated film was not damaged at all was indicated as ◯, the case where the plated film was not peeled off, but the case where damage was observed was indicated as Δ, and the case where the plated film was peeled off was indicated as x.

（４）曲げ加工性
曲げ加工性の評価は、ＪＩＳ Ｚ２２４８に準拠し、曲げ半径０．３ｍｍにて９０度Ｖ曲げ試験を行い、曲げた先端部表面を光学顕微鏡に観察することによって行った。かかる評価においては、しわが無いものをＡ、しわが小さいものをＢ、しわが大きいものをＣ、割れが小さいものをＤ、割れが大きいものをＥとして表した。
（５）半田付け性
半田付け性の評価は、酸洗いした銅合金にフラックスを塗付し、６０質量％のＳｎ及び４０質量％のＰｂからなる半田に、浴温条件２３５℃で５秒間浸漬させ、引き上げた後の試料表面を目視で観察することによって行った。かかる評価においては、試料表面に半田が均一に濡れたものを○、試料表面に半田が濡れているが、半田の広がりが不均一であり凹凸があったものを△、試料表面に半田が濡れなかった部分があったものを×として表した。 (4) Bending workability The bending workability was evaluated by performing a 90-degree V bending test at a bending radius of 0.3 mm in accordance with JIS Z2248 and observing the bent tip surface with an optical microscope. In this evaluation, A with no wrinkles, B with small wrinkles, C with large wrinkles, D with small cracks, and E with large cracks.
(5) Solderability Evaluation of solderability is performed by applying a flux to a pickled copper alloy and immersing in a solder composed of 60% by mass of Sn and 40% by mass of Pb at a bath temperature condition of 235 ° C. for 5 seconds. The sample surface was pulled up and observed visually. In such an evaluation, the sample surface with the solder uniformly wet is marked with ○, the sample surface is wet with solder, but the solder spread is uneven and the surface is uneven, and the sample surface with the solder wetted. Those where there was no part were expressed as x.

［実施例１］
実施例１では、Ｃｕ、Ｃｏ、Ｓｉ及び不可避的不純物を所定の組成比で含有する銅合金（本発明品１〜３）を図１に示すフローチャートに従って製造した。なお、Ｃｕの量については明示していないが、示された他の成分の量から見積もることが容易であることは言うまでもない。以下に、当該フローチャートを用いて銅合金の製造方法を具体的に説明する。
まず、表１に示す組成比を満たすように銅合金原料（Ｃｕ、Ｃｏ、Ｓｉ等）を準備し、当該銅合金原料を高周波溶解炉で溶解した後、厚さ１０ｍｍの板状の鋳塊に鋳造した（ステップＳ１）。
次に、鋳塊表面のスケールを除去するために面削を行った（ステップＳ２）。
次に、鋳塊を室温で圧延し、そして８００℃で焼鈍した後、さらにもう一度、室温で圧延して、厚さ０．３８ｍｍの薄板を作製した（ステップＳ３）。
その後、薄板を、９５０℃で２分間加熱した後、水中で冷却することによって溶体化処理を施した（ステップＳ４）。
次に、薄板を、５００℃で４時間加熱することによって時効処理を施した（ステップＳ５）。
次に、薄板を、１０℃／ｈ以上５０℃／ｈ以下の冷却速度（具体的には、表１に示す各冷却速度）で３８０℃まで冷却した（ステップＳ６）。
その後、薄板を、冷間圧延（仕上げ圧延）を行い、厚さ０．３ｍｍの銅合金を得た（ステップＳ７）。
なお、かかる実施例における最終冷間加工率はいずれも２１％であった。 [Example 1]
In Example 1, copper alloys (present invention products 1 to 3) containing Cu, Co, Si and unavoidable impurities in a predetermined composition ratio were manufactured according to the flowchart shown in FIG. Although the amount of Cu is not clearly shown, it goes without saying that it is easy to estimate from the amounts of the other components shown. Below, the manufacturing method of a copper alloy is demonstrated concretely using the said flowchart.
First, a copper alloy raw material (Cu, Co, Si, etc.) is prepared so as to satisfy the composition ratio shown in Table 1, and after the copper alloy raw material is melted in a high-frequency melting furnace, it is formed into a plate-shaped ingot having a thickness of 10 mm. Casting (step S1).
Next, chamfering was performed to remove the scale on the ingot surface (step S2).
Next, the ingot was rolled at room temperature, annealed at 800 ° C., and then rolled again at room temperature to produce a thin plate having a thickness of 0.38 mm (step S3).
Thereafter, the thin plate was heated at 950 ° C. for 2 minutes, and then subjected to a solution treatment by cooling in water (step S4).
Next, the thin plate was subjected to an aging treatment by heating at 500 ° C. for 4 hours (step S5).
Next, the thin plate was cooled to 380 ° C. at a cooling rate of 10 ° C./h or more and 50 ° C./h or less (specifically, each cooling rate shown in Table 1) (step S6).
Thereafter, the thin plate was subjected to cold rolling (finish rolling) to obtain a copper alloy having a thickness of 0.3 mm (step S7).
In addition, the final cold working rate in this Example was 21% in all cases.

［実施例２］
実施例２では、Ｃｕ、Ｃｏ、Ｓｉ、Ｚｎ及び不可避的不純物を所定の組成比で含有する銅合金（本発明品４〜７）を図１に示すフローチャートに従って製造した。
かかる実施例の製造条件は、実施例１と同じである。なお、かかる比較例における最終冷間加工率はいずれも２１％であった。 [Example 2]
In Example 2, copper alloys (invention products 4 to 7) containing Cu, Co, Si, Zn, and inevitable impurities in a predetermined composition ratio were manufactured according to the flowchart shown in FIG.
The manufacturing conditions of this example are the same as those of Example 1. Note that the final cold working rate in the comparative example was 21%.

［比較例１］
比較例１では、Ｃｕ、Ｃｏ、Ｓｉ及び不可避的不純物を含有するが、組成比が所定の範囲外である銅合金（比較品１〜４）を図１に示すフローチャートに従って製造した。
かかる比較例の製造条件は、実施例１と同じである。なお、かかる比較例における最終冷間加工率はいずれも２１％であった。
［比較例２］
比較例２では、Ｃｕ、Ｃｏ、Ｓｉ、Ｚｎ及び不可避的不純物を所定の組成比で含有するが、時効処理後の冷却速度が５℃／ｈである銅合金（比較品５）を図１に示すフローチャートに従って製造した。
かかる比較例の製造条件は、時効処理後の冷却速度を５℃／ｈとしたこと以外は、実施例１と同じである。なお、かかる比較例における最終冷間加工率は２１％であった。
実施例１及び２、並びに比較例１及び２で得られた銅合金における引張強度、導電率及びメッキ密着性の評価結果を表１に示す。また、かかる銅合金の引張強度と導電率との関係を図２に示す。 [Comparative Example 1]
In Comparative Example 1, copper alloys (comparative products 1 to 4) containing Cu, Co, Si, and inevitable impurities but having a composition ratio outside the predetermined range were manufactured according to the flowchart shown in FIG.
The manufacturing conditions of this comparative example are the same as those in Example 1. Note that the final cold working rate in the comparative example was 21%.
[Comparative Example 2]
In Comparative Example 2, a copper alloy (Comparative Product 5) containing Cu, Co, Si, Zn and unavoidable impurities at a predetermined composition ratio but having a cooling rate of 5 ° C./h after aging treatment is shown in FIG. Manufactured according to the flowchart shown.
The manufacturing conditions of this comparative example are the same as those of Example 1 except that the cooling rate after the aging treatment is 5 ° C./h. In addition, the final cold working rate in this comparative example was 21%.
Table 1 shows the evaluation results of tensile strength, electrical conductivity, and plating adhesion in the copper alloys obtained in Examples 1 and 2 and Comparative Examples 1 and 2. Moreover, the relationship between the tensile strength of this copper alloy and electrical conductivity is shown in FIG.

Figure 2008056977
Figure 2008056977

表１及び図２に示されるように、本発明品１〜７の銅合金はいずれも、介在物の最大サイズが２μｍ以下、容積比が０．５容積％以下であり、７００Ｎ／ｍｍ２以上の引張強度及び６０％ＩＡＣＳ以上の導電率を有していた。
また、本発明品２の銅合金は、Ｚｎを含有していないにも関わらず、良好なメッキ密着性を有していた。なお、本発明品１及び３の銅合金は、メッキ膜の剥離が生じなかった。
さらに、本発明品４〜７の銅合金は、Ｚｎを含有しているので、良好なメッキ密着性を有していた。
これに対して、比較品１及び３の銅合金は、Ｃｏ又はＳｉの量が少なすぎるために、十分なＣｏ２Ｓｉ化合物が析出せず、所望の引張強度が得られなかった。
また、比較品２の銅合金は、Ｃｏの量が多すぎるために、余剰Ｃｏによる好ましくない化合物相の発生によって介在物の量及び大きさが増大してしまい、所望の引張強度及び導電率が得られないと共に、メッキ密着性が悪かった。同様に、比較品４の銅合金は、Ｓｉの量が多すぎるために、余剰Ｓｉによる好ましくない化合物相が発生し、所望の導電率が得られなかった。
さらに、比較品５の銅合金は、時効処理後の冷却速度が遅すぎるために、介在物の最大サイズが４．５μｍと粗大化すると共にその容積比が０．７％と多くなり、所望の引張強度が得られなかった。 As shown in Table 1 and FIG. 2, all of the copper alloys of the inventive products 1 to 7 have a maximum inclusion size of 2 μm or less, a volume ratio of 0.5% by volume or less, and 700 N / mm 2 or more. And had a conductivity of 60% IACS or higher.
Moreover, although the copper alloy of this invention product 2 did not contain Zn, it had favorable plating adhesiveness. In addition, peeling of the plating film did not occur in the copper alloys of the inventive products 1 and 3.
Furthermore, since the copper alloys of the inventive products 4 to 7 contained Zn, they had good plating adhesion.
On the other hand, in the copper alloys of Comparative products 1 and 3, the amount of Co or Si was too small, so that a sufficient Co 2 Si compound was not precipitated and the desired tensile strength was not obtained.
Moreover, since the copper alloy of the comparative product 2 has too much Co, the amount and size of inclusions increase due to the generation of an undesirable compound phase due to excess Co, and the desired tensile strength and electrical conductivity are increased. It was not obtained and the plating adhesion was poor. Similarly, in the copper alloy of Comparative Product 4, since the amount of Si was too large, an undesirable compound phase due to excess Si was generated, and the desired conductivity was not obtained.
Furthermore, since the copper alloy of the comparative product 5 is too slow in the cooling rate after the aging treatment, the maximum size of the inclusion is coarsened to 4.5 μm and the volume ratio is increased to 0.7%, which is desired. Tensile strength was not obtained.

［実施例３］
実施例３では、Ｃｕ、Ｃｏ、Ｓｉ、Ｚｎ及び不可避的不純物と、Ｆｅ、Ｎｉ、Ｐ、Ｓｎ、Ｍｇ、Ｚｒ、Ｃｒ又はＭｎのうちの１種以上とを所定の組成比で含有する銅合金（本発明品８〜３８）を図１に示すフローチャートに従って製造した。かかる実施例の製造条件は、表２に示す組成比を用いたこと及び冷却速度を３０℃／ｈとしたこと以外は、実施例１と同じである。なお、かかる比較例における最終冷間加工率はいずれも２１％であった。
実施例３で得られた銅合金における引張強度、導電率、メッキ密着性及び曲げ加工性の評価結果を表２に示す。 [Example 3]
In Example 3, a copper alloy containing Cu, Co, Si, Zn, unavoidable impurities, and one or more of Fe, Ni, P, Sn, Mg, Zr, Cr, or Mn in a predetermined composition ratio (Invention products 8 to 38) were produced according to the flowchart shown in FIG. The production conditions of this example are the same as those of Example 1 except that the composition ratio shown in Table 2 was used and the cooling rate was 30 ° C./h. Note that the final cold working rate in the comparative example was 21%.
Table 2 shows the evaluation results of the tensile strength, electrical conductivity, plating adhesion and bending workability of the copper alloy obtained in Example 3.

Figure 2008056977
Figure 2008056977

表２に示されているように、本発明品８〜３８の銅合金はいずれも、介在物の最大サイズが２μｍ以下、容積比が０．５容積％以下であり、７００Ｎ／ｍｍ２以上の引張強度及び６０％ＩＡＣＳ以上の導電率を有していた。
また、本発明品８〜３８の銅合金はいずれも、Ｚｎを含有しているので、良好なメッキ密着性を有していた。
さらに、本発明品９〜１０、１２〜１３、３２〜３３及び３７〜３８の銅合金は、所定量のＦｅ又はＮｉの添加によって結晶粒が微細化されるために、曲げ加工性に優れていた。 As shown in Table 2, all of the copper alloys of the products 8 to 38 of the present invention have a maximum inclusion size of 2 μm or less, a volume ratio of 0.5% by volume or less, and 700 N / mm 2 or more. It had a tensile strength and a conductivity of 60% IACS or higher.
Moreover, since all the copper alloys of the products 8 to 38 of the present invention contained Zn, they had good plating adhesion.
Furthermore, the copper alloys of the present invention products 9 to 10, 12 to 13, 32 to 33 and 37 to 38 are excellent in bending workability because the crystal grains are refined by adding a predetermined amount of Fe or Ni. It was.

［実施例４］
実施例４では、Ｃｕ、Ｃｏ、Ｓｉ及び不可避的不純物を所定の組成比で含有し、且つＯ２含有量が１０ｐｐｍ以下及びＨ２含有量が１ｐｐｍ以下である銅合金（本発明品３９）、Ｃｕ、Ｃｏ、Ｓｉ及び不可避的不純物を所定の組成比で含有し、且つＯ２含有量が１０ｐｐｍ超過及びＨ２含有量が１ｐｐｍ以下である銅合金（本発明品４０）、Ｃｕ、Ｃｏ、Ｓｉ及び不可避的不純物を所定の組成比で含有し、且つＯ２含有量が１０ｐｐｍ超過及びＨ２含有量が１ｐｐｍ超過である銅合金（本発明品４１）を図１に示すフローチャートに従って製造した。本発明品３９の製造条件は、原料を溶解した溶湯中にＡｒガスを吹き込むことにより脱ガスを施したこと以外は、実施例１と同じである。また、本発明品４０及び４１の製造条件は、実施例１と同じである。なお、かかる実施例における最終冷間加工率はいずれも２１％であった。
実施例４で得られた銅合金における引張強度、導電率、メッキ密着性及び半田付け性の評価結果を表３に示す。 [Example 4]
In Example 4, a copper alloy (present product 39) containing Cu, Co, Si and unavoidable impurities in a predetermined composition ratio and having an O 2 content of 10 ppm or less and an H 2 content of 1 ppm or less, A copper alloy (present product 40) containing Cu, Co, Si and inevitable impurities in a predetermined composition ratio, an O 2 content exceeding 10 ppm and an H 2 content being 1 ppm or less, Cu, Co, Si A copper alloy (invention product 41) containing inevitable impurities in a predetermined composition ratio, having an O 2 content exceeding 10 ppm and an H 2 content exceeding 1 ppm was produced according to the flowchart shown in FIG. The production conditions of the product 39 of the present invention are the same as those in Example 1 except that degassing was performed by blowing Ar gas into the molten metal in which the raw material was dissolved. The manufacturing conditions of the products 40 and 41 of the present invention are the same as those in the first embodiment. In addition, the final cold working rate in this Example was 21% in all cases.
Table 3 shows the evaluation results of the tensile strength, electrical conductivity, plating adhesion and solderability of the copper alloy obtained in Example 4.

Figure 2008056977
Figure 2008056977

表３に示されるように、本発明品３９〜４１の銅合金はいずれも、介在物の最大サイズが２μｍ以下、容積比が０．５容積％以下であり、７００Ｎ／ｍｍ２以上の引張強度及び６０％ＩＡＣＳ以上の導電率を有していた。さらに、本発明品３９の銅合金は、５００時間及び１０００時間のメッキ密着性、並びに半田付け性が優れていた。この結果から、銅合金中のＯ２含有量を１０ｐｐｍ以下、及びＨ２含有量を１ｐｐｍ以下とすることによって、メッキ密着性及び半田付け性が向上することがわかる。 As shown in Table 3, the copper alloys of the inventive products 39 to 41 all have a maximum inclusion size of 2 μm or less, a volume ratio of 0.5% by volume or less, and a tensile strength of 700 N / mm 2 or more. And conductivity of 60% IACS or higher. Furthermore, the copper alloy of the product 39 of the present invention was excellent in plating adhesion and solderability for 500 hours and 1000 hours. From this result, it is understood that the plating adhesion and solderability are improved by setting the O 2 content in the copper alloy to 10 ppm or less and the H 2 content to 1 ppm or less.

以上のことからわかるように、本発明の銅合金は、強度及び導電性の両方に優れた、すなわち、７００Ｎ／ｍｍ２以上の引張強度及び６０％ＩＡＣＳ以上の導電率を有している。また、本発明の銅合金の製造方法は、７００Ｎ／ｍｍ２以上の引張強度及び６０％ＩＡＣＳ以上の導電率を有する銅合金を製造することができる。 As can be seen from the above, the copper alloy of the present invention is excellent in both strength and conductivity, that is, has a tensile strength of 700 N / mm 2 or more and a conductivity of 60% IACS or more. The method for producing a copper alloy of the present invention can produce a copper alloy having a tensile strength of 700 N / mm 2 or more and a conductivity of 60% IACS or more.

本発明の銅合金の製造方法を説明するフローチャートである。It is a flowchart explaining the manufacturing method of the copper alloy of this invention. 実施例１及び２、並びに比較例１及び２で得られた銅合金の引張強度と導電率との関係を示すグラフである。It is a graph which shows the relationship between the tensile strength of the copper alloy obtained by Example 1 and 2, and Comparative Examples 1 and 2, and electrical conductivity.

Claims (8)

０．８質量％以上１．８質量％以下のＣｏ及び０．１６質量％以上０．６質量％以下のＳｉを含有し、残部がＣｕ及び不可避的不純物で構成される銅合金であって、
前記Ｃｏと前記Ｓｉとの質量比（Ｃｏ／Ｓｉ）が３．０以上５．０以下であると共に、前記銅合金中に析出する介在物の大きさが２μｍ以下であり、且つ前記銅合金における０．０５μｍ以上２μｍ以下の大きさの介在物が０．５容積％以下であることを特徴とする銅合金。 A copper alloy containing 0.8 mass% or more and 1.8 mass% or less of Co and 0.16 mass% or more and 0.6 mass% or less of Si, with the balance being Cu and inevitable impurities,
The mass ratio of Co to Si (Co / Si) is 3.0 or more and 5.0 or less, and the size of inclusions precipitated in the copper alloy is 2 μm or less, and in the copper alloy A copper alloy, wherein inclusions having a size of 0.05 μm or more and 2 μm or less are 0.5% by volume or less. ０．１質量％以上１．０質量％以下のＺｎをさらに含有することを特徴とする請求項１に記載の銅合金。   The copper alloy according to claim 1, further comprising 0.1% by mass or more and 1.0% by mass or less of Zn. Ｆｅ、Ｎｉ、Ｐ、Ｓｎ、Ｍｇ、Ｚｒ、Ｃｒ又はＭｎのうちの１種以上を総量で０．０１質量％以上０．２質量％以下さらに含有することを特徴とする請求項１又は２に記載の銅合金。   The composition further comprises at least one of Fe, Ni, P, Sn, Mg, Zr, Cr, or Mn in a total amount of 0.01% by mass or more and 0.2% by mass or less. The described copper alloy. Ｏ２含有量が１０ｐｐｍ以下、及びＨ２含有量が１ｐｐｍ以下であることを特徴とする請求項１〜３のいずれか一項に記載の銅合金。 The copper alloy according to any one of claims 1 to 3, wherein the O 2 content is 10 ppm or less and the H 2 content is 1 ppm or less. （ａ）０．８質量％以上１．８質量％以下のＣｏ及び０．１６質量％以上０．６質量％以下のＳｉを含有し、残部がＣｕ及び不可避的不純物で構成され、且つ前記Ｃｏと前記Ｓｉとの質量比（Ｃｏ／Ｓｉ）が３．０以上５．０以下である銅合金原料を溶解して鋳塊を形成した後、前記鋳塊を圧延する工程と、
（ｂ）前記圧延材を７００℃以上１０００℃以下に加熱した後に急冷する溶体化処理を施す工程と、
（ｃ）前記溶体化処理後の合金素材を４００℃以上６００℃以下で２時間以上８時間以下加熱する時効処理を施す工程と、
（ｄ）前記時効処理後の合金素材を、少なくとも３８０℃までは１０℃／ｈ以上５０℃／ｈ以下の冷却速度で冷却する工程と、
（ｅ）前記冷却後の合金素材を冷間圧延して仕上げる工程と
を含むことを特徴とする銅合金の製造方法。 (A) 0.8% by mass or more and 1.8% by mass or less of Co and 0.16% by mass or more and 0.6% by mass or less of Si, with the balance being composed of Cu and inevitable impurities, and the Co And a step of rolling the ingot after melting a copper alloy raw material having a mass ratio (Co / Si) of 3.0 to 5.0 and forming an ingot;
(B) applying a solution treatment for rapidly cooling the rolled material after heating to 700 ° C. or higher and 1000 ° C. or lower;
(C) performing an aging treatment in which the alloy material after the solution treatment is heated at 400 ° C. to 600 ° C. for 2 hours to 8 hours;
(D) a step of cooling the alloy material after the aging treatment at a cooling rate of 10 ° C./h or more and 50 ° C./h or less to at least 380 ° C .;
And (e) a process of cold rolling the alloy material after cooling to finish the copper alloy manufacturing method. 前記銅合金原料が、０．１質量％以上１．０質量％以下のＺｎをさらに含有することを特徴とする請求項５に記載の銅合金の製造方法。   The said copper alloy raw material further contains 0.1 to 1.0 mass% Zn further, The manufacturing method of the copper alloy of Claim 5 characterized by the above-mentioned. 前記銅合金原料が、Ｆｅ、Ｎｉ、Ｐ、Ｓｎ、Ｍｇ、Ｚｒ、Ｃｒ又はＭｎのうちの１種以上を総量で０．０１質量％以上０．２質量％以下さらに含有することを特徴とする請求項５又は６に記載の銅合金の製造方法。   The copper alloy raw material further contains at least one of Fe, Ni, P, Sn, Mg, Zr, Cr, or Mn in a total amount of 0.01% by mass to 0.2% by mass. The manufacturing method of the copper alloy of Claim 5 or 6. 前記銅合金原料は、Ｏ２含有量が１０ｐｐｍ以下、及びＨ２含有量が１ｐｐｍ以下であることを特徴とする請求項５〜７のいずれか一項に記載の銅合金の製造方法。 The copper alloy material is, O 2 content of 10ppm or less, and a manufacturing method of the copper alloy according to any one of claims 5 to 7 containing H 2 content is equal to or is 1ppm or less.
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US20140369883A1 (en) 2014-12-18

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